Photoluminescence spectroscopy of the CN radical produced in the infrared photolysis of CH3CN

The infrared laser-induced photolysis of CH₃CN has been studied by observing luminescence from the excited CN (B²Σ⁺) radical and pulsed dye laser-induced fluorescence of ground state CN(X²Σ⁺), both produced as primary fragments. Both temporal and wavelength resolved spectroscopy have been performed on the luminescence, whereas pulsed dye laser probing has allowed time-resolution of the CN(X²Σ⁺) radical as well as measurements of the decay time of the CN(B²Σ⁺) state produced in the dye laser pumping. A reaction mechanism, characterizing the observed results, is proposed.     

Infrared multiphoton excitation of SO2 to fluorescent states

SO₂ molecules excited under essentially collision-free conditions by intense (>20 G/Wcm²) CO₂ laser pulses give off a broad UV—visible luminescence through inverse electronic relaxation. Unlike in larger polyatomics, the infrared multiphoton excitation process is controlled by the laser intensity and not the laser fluence.     

CO2 laser excitation of triethylsilane: Time resolved luminescence of diethylsilyl radical

The infrared multiphoton excitation of triethylsilane in the gas phase, with a pulsed CO₂ laser at high intensities (I > 700 MW/cm²), produced an intense luminescence. The spectrum and time profile of this luminescence was studied as a function of pressure, and laser frequency. The radiative lifetime of this emission was 357 ± 10 ns, and the quenching rates by Cl₂ and NO were determined from lifetime measurements. A reasonable mechanism for the interpretation of this luminescence involves the initial infrared multiphoton decomposition of triethylsilane, followed by the secondary infrared multiphoton excitation of the primary photofragment diethylsilyl radical, which subsequently undergoes relaxation to an excited electronic state. The addition of O₂ resulted in a new chemiluminescence at shorter wavelengths, which corresponds to the SiO* chromophore group. © 1994 John Wiley & Sons, Inc.     

Multimode Luminescence Tailoring and Improvement of Cs2NaHoCl6 Cryolite Crystals via Sb3+/Yb3+ Alloying for Versatile Photoelectric Applications

Lead-free halide double perovskites are currently gaining significant attention owing to their exceptional environmental friendliness, structural adjustability as well as self-trapped exciton emission. However, stable and efficient double perovskite with multimode luminescence and tunable spectra are still urgently needed for multifunctional photoelectric application. Herein, holmium based cryolite materials (Cs₂NaHoCl₆) with anti-thermal quenching and multimode photoluminescence were successfully synthesized. By the further alloying of Sb³⁺ (s-p transitions) and Yb³⁺ (f-f transitions) ions, its luminescence properties can be well modulated, originating from tailoring band gap structure and enriching electron transition channels. Upon Sb³⁺ substitution in Cs₂NaHoCl₆, additional absorption peaking at 334 nm results in the tremendous increase of photoluminescence quantum yield (PLQY). Meanwhile, not only the typical NIR emission around 980 nm of Ho³⁺ is enhanced, but also the red and NIR emissions show a diverse range of anti-thermal quenching photoluminescence behaviors. Furthermore, through designing Yb³⁺ doping, the up-conversion photoluminescence can be triggered by changing excitation laser power density (yellow-to-orange) and Yb³⁺ doping concentration (red-to-green). Through a combined experimental-theoretical approach, the related luminescence mechanism is revealed. In general, by alloying Sb³⁺/Yb³⁺ in Cs₂NaHoCl₆, abundant energy level ladders are constructed and more luminescence modes are derived, demonstrating great potential in multifunctional photoelectric applications.     

Strychnine : A fast physical quencher of singlet oxygen (1Δg)

Pulsed laser excitation of 2-acetonaphthone in aerated benzene, toluene, acetone, acetonitrile or ethanol results in formation of O₂(¹Δ_g), the infrared luminescence of which has been monitored by time-resolved emission spectroscopy. The rate constants for the quenching of this emission by the indole alkaloid strychnine in all five solvents have been determined and compared with the corresponding values for the well-known O₂ (¹Δ_g) quencher DABCO. Strychnine (1) is the fastest known tertiary amine quencher of this species via a process which is at least 99% physical in character.     

Novel Eu-doped lead telluroborate glasses for red laser source applications

We report the absorption, luminescence and decay analysis of Eu³⁺-doped lead telluroborate (PTBEu) glasses for different Eu³⁺ concentrations ranging from 0.1 to 2.0 mol%. Judd-Ofelt intensity parameters obtained from ⁵D₀→⁷F_J=0-6 emission transitions of Eu³⁺ were used to calculate the radiative transition probabilities, luminescence branching ratios and radiative decay times. The luminescence spectra and decay times were measured at 464 nm excitation. The optical band gap energies are also determined. The luminescence intensity ratio, color purity and emission cross-section values support that the PTBEu20 glass is a suitable candidate for red laser source applications.     

Luminescence spectrum and kinetics of laser-excited HgNH3 complex

When an Hg/NH₃ gas mixture was irradiated by laser light around 260 nm, luminescence appeared in the range of 290–360 nm. The spectrum of the luminescence was almost the same as that induced by the Hg photosensitized reaction of NH₃, and thus, the laser-induced luminescence was assigned to emission of an excited HgNH₃ complex. The luminescence spectrum as well as the excitation spectrum could be reproduced by the Franck-Condon factors calculated from the bound-free transition between the Hg-NH₃ repulsive ground state and the excited bound state. Time-evolution measurements on the luminescence induced by the pulsed irradiation of the laser indicated that initially formed HgNH₃ excimer had to make a collisional transition to a state which could emit the luminescence around 340 nm.     

Evidence for the cation radical DPA+ as an intermediate in the luminescent cathodic reduction of 9,10-dichloro-9,10-dihydro-9, 10-diphenylanthracene

The influence of 20 aromatic amines or carbazoles D and 14 carbonyl compounds A on the cathodic luminescence of 9,10-dichloro-9,10-dihydro-9,10-diphenylanthracene, DPACl₂, was investigated in DMF at a rotating platinum disk electrode. The cathodically generated oxidizing agent in the energy sufficient electron transfer luminescence mechanism is intercepted by D if E_1/1^0x(D) is more negative than +1.3 V (SCE). The emission of DPA is also observed if DPACl₂ is reduced by the anion radicals of the non-luminescent compounds A. This result proves the participation of DPA⁺ in the luminescence process. A one-step fractionation of DPACl₂ by A^? into DPA⁺ and 2 Cl^? is proposed as a mechanism of the formation of this strong oxidizing intermediate in a reduction process. The threshold reduction potential of A in this reaction is about ?1.15 V.     

Green and red upconversion luminescence in CeO2:Er powders produced by 785 nm laser

CeO₂:Er³⁺ powders were prepared by Pechini type sol-gel method. The structural properties of CeO₂:Er³⁺ were studied by X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) spectra. The results show that CeO₂:Er³⁺ has low phonon cutoff energy, which indicate that CeO₂:Er³⁺ may have high luminescent efficiency. The green and red upconverted luminescence spectra of Er³⁺ were investigated under excitation into the ⁴I_9/2 level by 785 nm laser. The upconversion mechanisms were studied in detail through laser power dependence and Er³⁺ ions concentration dependence of upconverted emissions, and results show that excited state absorption and energy transfer process are the possible mechanisms for the upconversion. The upconversion properties indicate that CeO₂:Er³⁺ may be used in upconversion phosphors.     

Laser intensity effects in the IR multiple-photon absorption of OsO4

The visible luminescence resulting from multiple-photon absorption of CO₂ laser radiation in OsO₄ depends upon the laser intensity as well as fluence. The use of single-mode laser pulses, shaped by electro-optic crystal switching, has enabled this intensity dependence to be determined quantitatively.     

New vibronic bands of CH2 observed in a pulsed supersonic jet

Spectroscopic studies of the methylene radical in a supersonic expansion have resulted in the observation of previously unreported CH₂ B?¹ B₁ ← ã¹A₁, hot band transitions. These ã state levels are populated by radiative cascade following multiphoton dissociation of ketene. Multiphoton excitation of ketene is also found to produce a diffuse luminescence with a lifetime longer than 50 μs. The conclusion of Lengel and Zare are singlet methylene is not produced one-photon nitrogen laser photolysis of cold ketene is confirmed.     

Singlet Oxygen Luminescence Image in Blood Vessels During Vascular-Targeted Photodynamic Therapy

Singlet oxygen (¹O₂) is widely regarded as the main cytotoxic substance that induces the biological damage for photodynamic therapy (PDT). In this study, the previously developed near-infrared (NIR) optical imaging system was optimized for fast imaging of ¹O₂ luminescence. The optical imaging system enables direct imaging of ¹O₂ luminescence in blood vessels within 2 s during vascular-targeted PDT (V-PDT), which makes this system extremely practical for in vivo studies. The dependence of RB concentration on ¹O₂ luminescence image was investigated for V-PDT, and the data imply that 1270 nm signal is attributed to ¹O₂ luminescence. The imaging system operates with a field of view of 9.60 × 7.68 mm² and a spatial resolution of 30 μm, which holds the potential to elucidate the correlation between cumulative ¹O₂ luminescence and vasoconstriction for V-PDT.     

Singlet-Oxygen Quenching by Carotenoids: Steady-state luminescence experiments

The near-infrared luminescence of singlet oxygen (¹O₂) has been measured in order to determine the efficiency of ¹O₂ quenching by two carotenoid compounds, β-carotene and canthaxanthin. 1H-Phenalen-1-one and rose bengal have been used as photosensitizers in those steady-state luminescence experiments. Stern-Volmer analysis of the ¹O₂ luminescence in solutions of CCl₄ and CD₃OD, containing different concentrations of the carotenoids, has shown a very efficient quenching by canthaxanthin. The rate constants are about a factor of 2 below the diffusion limited values for the given solvents, confirming earlier results in benzene. In comparison, the efficiency of ¹O₂ quenching by β-carotene is slightly lower than that by canthaxanthin in non-polar solvents and is reduced by an order of magnitude in CD₃OD, due to the aggregation of this quencher.     

Laser-induced luminescence of barite after thermal treatment

The photoluminescence (PL) of barite is a noncharacteristic property and cannot be used for the investigation of its structure. After thermal treatment of barite at 600°C several luminescent centers were observed, providing information about different impurities. UO ₂ ²⁺ was determined from the vibrational structure and the long decay time of the luminescence band. Two different types of uranyl were detected, thin films of uranyl mineral (most probably, reserfordin) and a solid solution of uranyl ion in barite crystal. Characteristic green luminescence of UO ₂ ²⁺ may be used as indicative feature for the prospecting of uranium deposits and for the sorting of barite ores with the aim of cleaning from harmful U impurities. Eu²⁺ was determined from the spectral position, the half-width and the characteristic decay time of the luminescence band. Mn²⁺ and Ag⁺ were determined by comparing luminescence bands spectral parameters to those of synthesized BaSO₄−Mn and BaSO₄−Ag. Fe³⁺ or Mn⁴⁺ were determined from the spectral-kinetic parameters of the luminescence bands. Dedicated to Professor Lisa Heller-Kallai on the occasion of her 65^th birthday     

Luminescence of cesium dicyanoaurate(I). Evidence for extended Au(I)Au(I) interactions in two dimensions

The luminescence of microcrystalline samples of Cs[Au(CN)₂] is reported and ascribed to planar AuAu interactions. Low-temperature measurements from 1.6 to 100 K of the luminescence decay rate of Cs[Au(CN)₂] for the band centered at 458 nm reveal the presence of at least two emitting levels separated by 46 cm⁻¹. A simple orbital model is proposed to account for the luminescence, and spin—orbit coupling is invoked to explain the splitting of the two lowest states. The analogies and differences between this luminescence and that observed for salts of Pt(CN)₄²⁻ are briefly discussed.     

Low temperature spectroscopy of europium perchlorate in non-aqueous solutions. The steric effect studies

The laser excited luminescence spectra of the Eu³⁺ ion were used to study equilibrium solvatation processes in non-aqueous solutions.The luminescence observed was mainly from ⁵D₀ excited states to the ⁷F_J ground levels. The fine structure observed within these emission bands leads to the determination of the site symmetry of the Eu³⁺ species in solution.Analysis of the ƒ—ƒ transition probability, based on the Judd theory, leads to Ω_λ parameter determinations.Intensity analysis of the ⁷F₀→⁵D₂ transition allows us to consider the steric effect on the structure of n-propanol and i-propanol solvates.     

A New Copper(I) Complex Based on Imidazole and Triphenylphosphine Ligands: Synthesis,Structure, Third‐Order NLO,and Fluorescence Properties

A new candidate [Cu(PPh₃)₂Him]Br ( 1 , PPh₃=triphenylphosphine, Him=1‐H‐imidazole) for nonlinear optical (NLO) materials has been synthesized and characterized crystallographically. The third‐order NLO optical properties were measured by the Z‐scan technique with an 8 ns pulsed laser at 532 nm. Compound 1 exhibits strong NLO absorptive abilities [α₂=(61±5)×10^?12] and effective self‐focusing performance [n₂=(15±3)×10^?18 m²·W^?1] in 1.01×10^?4 mol·dm^?3 DMF solution. The compound also exhibits luminescence in DMF solution at room temperature and shows narrow emission with maximum at 382 nm. The electronic structure and photoluminescent process were investigated by means of TD‐DFT calculations. The results suggest that the contribution to the frontier orbitals from the Cu? Br δ bond plays a crucial role in its linear optical properties, and the origin of luminescence is attributable to the π??→n transitions.     

Defective [Bi2O2]2+ Layers Exhibiting Ultrabroad Near-Infrared Luminescence

Aurivillius phases have been routinely known as excellent ferroelectrics and have rarely been deemed as materials that luminesce in the near-infrared (NIR) region. Herein, it is shown that the Aurivillius phases can demonstrate broadband NIR luminescence that covers telecommunication and biological optical windows. Experimental characterization of the model system Bi_2.14Sr_0.75Ta₂O_9−x, combined with theoretical calculations, help to establish that the NIR luminescence originates from defective [Bi₂O₂]²⁺ layers. Importantly, the generality of this finding is validated based on observations of a rich bank of NIR luminescence characteristics in other Aurivillius phases. This work highlights that incorporating defects into infinitely repeating [Bi₂O₂]²⁺ layers can be used as a powerful tool to space-selectively impart unusual luminescence emitters to Aurivillius-phase ferroelectrics, which not only offers an optical probe for the examination of defect states in ferroelectrics, but also provides possibilities for coupling of the ferroelectric property with NIR luminescence.     

Vacuum ultraviolet and near-infrared excited luminescence properties of Ca3(PO4)2:RE, Na (RE=Tb, Yb, Er, Tm, and Ho)

Tb³⁺, Yb³⁺, Tm³⁺, Er³⁺, and Ho³⁺ doped Ca₃(PO₄)₂ were synthesized by solid-state reaction, and their luminescence properties were studied by spectra techniques. Tb³⁺-doped samples can exhibit intense green emission under VUV excitation, and the brightness for the optimal Tb³⁺ content is comparable with that of the commercial Zn₂SiO₄:Mn²⁺ green phosphor. Under near-infrared laser excitation, the upconversion luminescence spectra of Yb³⁺, Tm³⁺, Er³⁺, and Ho³⁺ doped samples demonstrate that the red, green, and blue tricolored fluorescence could be obtained by codoping Yb³⁺-Ho³⁺, Yb³⁺-Er³⁺, and Yb³⁺-Tm³⁺ in Ca₃(PO₄)₂, respectively. Good white upconversion emission with CIE chromaticity coordinates (0.358, 0.362) is achieved by quadri-doping Yb³⁺-Tm³⁺-Er³⁺-Ho³⁺ in Ca₃(PO₄)₂, in which the cross-relaxation process between Er³⁺ and Tm³⁺, producing the ¹D₂-³F₄ transition of Tm³⁺, is found. The upconversion mechanisms are elucidated through the laser power dependence of the upconverted emissions and the energy level diagrams.     

Site Occupancies,Electron–Vibration Interaction and Energy Transfer of CaMgSi2O6: Eu2+, Mn2+ Phosphors for Potential Temperature-Sensing and Anti-counterfeiting Applications

Eu²⁺-, Mn²⁺- and Eu²⁺−Mn²⁺-doped CaMgSi₂O₆ phosphors have been prepared by a high-temperature solid-state reaction. Systematic investigation of the concentration- and temperature-dependent luminescence of Mn²⁺ showed that Mn²⁺ ions occupy two distinct sites in CaMgSi₂O₆. Electron–vibration interaction (EVI) analyses of Mn²⁺ ions revealed Huang–Rhys factors of 4.73 and 2.82 as well as effective phonon energies of 313 and 383 cm⁻¹ for the two sites. Eu²⁺−Mn²⁺ energy transfer is also discussed, and its efficiency is estimated by lifetime and luminescence spectra. The different thermal quenching behaviours of Eu²⁺ and Mn²⁺, the distinct emission colours of Eu²⁺ (blue, band peak at ∼451 nm) and Mn²⁺ (yellow–red range, band peaks at ∼583 and 693 nm) endow the co-doped samples with potential applications in luminescence thermometry and temperature-/excitation wavelength-responsive dual anti-counterfeiting.